CN101229513A - Supported palladium catalyst used for anthraquinone producing peroxid and preparing method thereof - Google Patents
Supported palladium catalyst used for anthraquinone producing peroxid and preparing method thereof Download PDFInfo
- Publication number
- CN101229513A CN101229513A CNA2007100629988A CN200710062998A CN101229513A CN 101229513 A CN101229513 A CN 101229513A CN A2007100629988 A CNA2007100629988 A CN A2007100629988A CN 200710062998 A CN200710062998 A CN 200710062998A CN 101229513 A CN101229513 A CN 101229513A
- Authority
- CN
- China
- Prior art keywords
- catalyst
- load type
- palladium catalyst
- palladium
- carrier
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Landscapes
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention provides a support palladium catalyst used for producing hydrogen peroxide through an anthraquinone process and a preparation method thereof. Principally, a hollow heterotype carrier is adopted to immerse the active constituent palladium before being baked, a carrier obtained is a hollow hereotype one, and the content of the active constituent palladium is 0.05 percent-0.7 percent of the support palladium catalyst. Meanwhile, the invention provides a method for adopting the catalyst to produce the hydrogen peroxide through the anthraquinone process. The catalyst of the invention is mainly applied to anthraquinone hydrogenation reaction when producing the hydrogen peroxide through the anthraquinone process, which can reduce the bed resistance and improve the production ability.
Description
Technical field
The present invention relates to a kind of Catalysts and its preparation method that hydrogen peroxide is used of producing, specifically be meant a kind of load type palladium catalyst that is used for process for prepairng hydrogen peroxide by anthraquinone and preparation method thereof.
Background technology
Hydrogen peroxide (hydrogen peroxide) is a kind of important Inorganic Chemicals, and the method for industrial production hydrogen peroxide mainly is anthraquinone.The main technique of process for prepairng hydrogen peroxide by anthraquinone is: the anthraquinone working solution and the hydrogen of certain proportioning are fed the hydrogenation tower, in the hydrogenation tower catalyst is housed, under the effect of catalyst, anthraquinone hydrogenation in the working solution generates anthrahydroquinone, again the working solution of this hydrogenation (hydride) is sent into oxidizing tower through after the gas-liquid separation, bubbling air (or oxygen) makes the anthrahydroquinone oxidation generate anthraquinone and hydrogen peroxide in the oxidizing tower, working solution after the oxidation (oxidation liquid) enters in the extraction tower, with deionized water the hydrogen peroxide that contains in the oxidation liquid is extracted, the aqueous hydrogen peroxide solution that obtains can obtain the hydrogen peroxide product through purified treatment, and the working solution after the extraction can be recycled after handling with activated alumina.
In the technology of process for prepairng hydrogen peroxide by anthraquinone, catalytic hydrogenation is unusual important step.In the hydrogenation tower, the catalytic hydrogenation reaction of anthraquinone is rapid, be accompanied by the hydrogenation of anthraquinone in the working solution, side reaction (degraded) also can take place in solvent as carrier in the working solution in process of production, also have the anthraquinone generation degradation reaction of part, and the hydrogenation catabolite is different with the difference of degree of hydrogenation, and may be attended by polymerisation, in a word, in actual industrial production, the side reaction in the hydrogenation tower is intricate, and degradation product is many, up to the present, the clear interpretation that can't make science to the mechanism and the generation rejection condition of these side reactions fully.These numerous and diverse side reactions hydrogenation efficiency from influenced reaction to a great extent, and the productive rate and the quality of the final hydrogen peroxide that generates of influence.From the suitability for industrialized production angle, any process reform all must be taken all factors into consideration the influence of many-sided factor, this also is the main cause that is difficult to have breakthrough for the research improvement of process for prepairng hydrogen peroxide by anthraquinone technology, in other words, for the catalyst of moulding and technological operation are attempted any improvement and all had very big risk relatively.
Hydrogenation catalyst is the key technical feature of anthraquinone hydrogenation catalysis always, has important function in the technology of process for prepairng hydrogen peroxide by anthraquinone.The catalyst of high activity and high selectivity can improve the production capacity of anthrahydroquinone and reduce the anthraquinone degraded, thereby improves the cyclic utilization rate of working solution, reduces to produce consuming.The technology of process for prepairng hydrogen peroxide by anthraquinone is through the differentiation of recent two decades, in most of industrial production, all adopt fixed bed reactors, and be catalyst with the load type palladium catalyst, most fixed-bed palladium catalysts technologies all adopt sphere or bar shaped supported carrier active component palladium to form (wherein palladium content is usually about 0.3%), though in industrial production, be extensive use of, but these catalyst are solid construction, increasing surface area is restricted, catalytic activity and selectivity are difficult to further raising, in the practical application in industry, solid catalyst bulk density is big, causes the beds load big after the filling, also can cause the increase of catalyst bed resistance in the reaction; On the other hand, the catalyst after the load similar " eggshell " structure, easily decortication in use, catalyst life is short, is subjected to the restriction of bed bearing capacity, and production capacity is difficult to improve, and causes anthraquinone unit consumption height.
Along with science and technology development, the application of hydrogen peroxide is increasingly extensive, and demand is also in continuous increase.If can improve the technology of producing hydrogen peroxide, boost productivity, and reduce production costs, will be of great immediate significance.
Summary of the invention
Main purpose of the present invention promptly is to provide a kind of new load type palladium catalyst, and this catalyst is used for the hydrogenation reaction of process for prepairng hydrogen peroxide by anthraquinone technology, can improve hydrogenation efficiency, and the catalyst cost is low.
Another object of the present invention is to provide a kind of method of the simple described load type palladium catalyst of preparation.
The present invention also provides a kind of method of process for prepairng hydrogen peroxide by anthraquinone, uses load type palladium catalyst of the present invention as the anthraquinone hydrogenation catalyst for reaction in this method, not only can improve reaction yield, has also saved catalyst amount.
At first, the invention provides a kind of load type palladium catalyst that is used for process for prepairng hydrogen peroxide by anthraquinone, the carrier of this catalyst is hollow special-shaped carrier, and the content of active component palladium is 0.05%～0.7% (wt).As the preferred embodiments of the invention, the content of active component palladium described in this catalyst is 0.2%～0.5% (wt).
" hollow special-shaped carrier " described in the present invention is meant to reducing the heap ratio, enlarging external surface area, and make the carrier that has suitable space in the body, as Raschig ring, θ ring, Wheel ring packing, porous bar, porous ring or the like shape, be seen as aspheric pelleted substrate with hollow-core construction from outward appearance, compare with corresponding full particle, its bulk density is lowered, outer surface enlarges markedly, be applicable in the hollow special-shaped carrier of the present invention that the so-called inner suitably shape and the rule in space do not have special requirement.
Need to prove: the shape of above-mentioned cited described hollow special-shaped carrier only is major electrical components, and selection of the present invention also not only that.The outside dimension of catalyst granules of the present invention is usually in the scope of 3mm～10mm, concrete size Selection can be determined according to conditions such as process conditions concrete in the practical application in industry, production capacity, for example, in the high large-scale reaction tower of production capacity, can suitably select the beaded catalyst of large-size, with intensity of suitable raising catalyst etc., this is readily appreciated that for a person skilled in the art and grasps.
According to specific embodiments of the present invention, in the catalyst of the present invention, described carrier can be silica, is preferably indefinite form silica, for example can be to contain quartzy indefinite form silica.Described carrier also can be the mixture of aluminium oxide or aluminium oxide and silica.The aluminium oxide that is used for catalyst carrier of the present invention can be γ-Al
2O
3, δ-Al
2O
3, θ-Al
2O
3, α-Al
2O
3, or their mixing phase; Preferably, catalyst of the present invention is to comprise α-Al
2O
3The mixing phase alumina be carrier.The inventor finds through a large amount of real application research, in the anthraquinone hydrogenation reaction, contains α-Al in the carrier of used loaded catalyst
2O
3The time, can limit the generation of side reaction, improve hydrogenation efficiency.
The present invention provides the preparation method of described load type palladium catalyst simultaneously, this preparation method compares with the preparation method of load type palladium catalyst of the prior art, process conditions do not have special change, mainly are to adopt hollow special-shaped carrier to substitute solid-core supports such as sphere of the prior art or bar shaped.For example, the preparation method of described load type palladium catalyst of the present invention can mainly may further comprise the steps:
Hollow special-shaped carrier is placed the palladium salting liquid, make it to flood active component palladium on request; Described palladium salt can be the aqueous solution of palladium bichloride or the aqueous solution of palladium, is preferably the aqueous solution of palladium;
Flooded carrier oven dry back roasting 2～6 hours (under the air atmosphere) in 400～600 ℃ of active component palladium, preferably, can obtain load type palladium catalyst of the present invention 500～550 ℃ of following roastings 3～4 hours.
Dipping process in this preparation process can be incipient impregnation or excessive dipping, and the concrete operations such as oven dry of the dipping of this carrier and dipping back carrier are routine techniques, and for example, bake out temperature can be 80～150 ℃, preferably 100～120 ℃ of oven dry.
The present invention also provides a kind of method of process for prepairng hydrogen peroxide by anthraquinone, mainly is to use load type palladium catalyst of the present invention as the anthraquinone hydrogenation catalyst for reaction in this method.Under the effect of load type palladium catalyst of the present invention, make anthraquinone hydrogenation generate anthrahydroquinone, anthrahydroquinone generates anthraquinone and hydrogen peroxide through oxidation again, separates through further purified treatment to obtain the hydrogen peroxide product.
The present invention uses, and to have hollow special-shaped carriers of shape such as Raschig ring, Wheel ring packing, θ ring, porous bar and/or porous ring all commercially available or produced on request by manufacturing enterprise, perhaps directly use silica and various things alumina packing mutually commonly used in the present chemical engineering industry, the present invention with these special-shaped fillers with hollow-core construction as carrier, to utilize the catalyst for preparing after its dipping active component to be used for the anthraquinone hydrogenation reaction, discovery can obtain beyond thought beneficial effect.Prove by a large amount of concrete application experiments, loaded catalyst of the present invention is owing to adopt hollow special-shaped carrier, be used for process for prepairng hydrogen peroxide by anthraquinone, hydrogenation efficiency significantly improves, filling quality in the production under the identical admission space reduces, bed resistance descends (the production pressure that reaches under the identical hydrogenation efficiency reduces), finally effectively reduces production cost.
The front chatted and, anthraquinone hydrogenation is produced the course of reaction of hydrogen peroxide and has been followed a large amount of side reactions usually, these are the principal elements that influence hydrogenation efficiency.The present invention adopts hollow special-shaped carrier to replace solid-core support supported active composition of the prior art, the catalyst outer surface that obtains increases, under the identical load amount, the catalyst heap is than descending, the palladium content of per volume of catalyst significantly descends, though can't sufficient evidence be arranged from mechanism, use catalyst of the present invention, filler and catalyst effect are organically combined, improved the mass-transfer efficiency in the hydrogenation reaction, given the present invention beyond thought beneficial effect, promptly, effectively solve the decortication of spheric catalyst in the prior art, bed resistance is big, production capacity is little, problems such as side reaction is serious, but by concrete application experiment checking, use catalyst of the present invention and carry out the anthraquinone hydrogenation reaction, under existing general industrial working condition, equivalent production capacity, under the equal degradation condition, can make the bed resistance descend more than 30% save catalyst weight 25%～30%.
The specific embodiment
Specify enforcement of the present invention and the beneficial effect that is had below by embodiment, but therefore the present invention is not subjected to any restriction.
Embodiment 1
Take by weighing 100 gram δ-Al
2O
3The Raschig ring carrier, be of a size of: outer shroud 4mm, interior ring 1.5mm, long 4mm is placed on (wherein containing palladium 0.3 restrains) in the 70ml palladium chloride aqueous solution, incipient impregnation 2 hours, washing removes the chlorion on the catalyst, about 100 ℃, dried about 3 hours then, and about 2 hours of 500 ℃ of left and right sides roastings, make palladium content and be 0.3% load type palladium catalyst, the about 0.5g/ml of bulk density.
Catalyst activity adopts micro fixed-bed reactor to estimate, and reactor is Φ 30 * 170mm, 50 ℃ of reaction temperatures, pressure 0.2MPa, catalyst loading amount 30ml, liquid air speed 12h
-1, hydrogen air speed 120h
-1, working solution effective anthraquinone concentration is 130g/l, uses hydrogen at 80 ℃ before the activity rating, hydrogen air speed 120h
-1Under reduce and became the hydrogenation working solution in 8 hours.
The mensuration of hydrogenation efficiency:
Get 5ml hydrogenation working solution in 500 milliliters of separatory funnels with pipette, add the phosphoric acid of 20ml aromatic hydrocarbons and 10 milliliter 10% again, the gas dispersion pipe is inserted wherein, about 15 minutes of logical dioxygen oxidation.With distilled water extraction hydrogen peroxide wherein, use 20 milliliters at every turn, coextraction 4 times is put into conical flask with lower aqueous solution, does not have hydrogen peroxide in extract.20 milliliters sulfuric acid are added in the above-mentioned extract, use the potassium permanganate standard solution titration, until the micro-redness of solution, 30 seconds the colour-fast terminal point that is.
Be calculated as follows hydrogenation efficiency (being called for short hydrogen imitates):
In the formula:
B--hydrogenation efficiency g/l
The concentration mol/l of C--potassium permanganate standard liquid
The V--titration consumes the volume ml of potassium permanganate
Evaluation result, the hydrogenation efficiency of present embodiment catalyst are 5.1g/l.
Embodiment 2
Take by weighing 100 the gram three orifice ring alumina supports, thing be mutually δ, θ and α mixing mutually, be of a size of: external diameter 8mm, diameter of bore 3mm, 120 ℃ of distributions of endoporus, high 4mm.The alumina support that takes by weighing is placed the 500g palladium aqueous solution (wherein containing palladium 0.5 gram), about 3 hours of excessive dipping, oven dry 2 hours about 140 ℃ then afterwards about 5 hours of 400 ℃ of left and right sides roastings, makes palladium content and is 0.5% load type palladium catalyst.Press the method for the evaluation of catalyst activity of record among the embodiment 1, the hydrogen effect that records the catalyst of present embodiment is 6.3g/l.
Embodiment 3
Take by weighing 100 gram θ ring indefinite form silica supports, outer shroud is 4mm, interior ring is 2mm, long 3mm places the aqueous solution (wherein contain palladium 0.2 gram) of 300 gram palladium bichlorides with this carrier, floods 5 hours, washing removes the chlorion on the catalyst, then about 3 hours of 80 ℃ of oven dry, about 2 hours of 600 ℃ of roastings make palladium content and are 0.2% load type palladium catalyst.
Press the method for the evaluation of catalyst activity of record among the embodiment 1, the hydrogen effect that records the catalyst of present embodiment is 3.58g/l.
Embodiment 4
The catalyst for preparing among the embodiment 1 is applied to the industrial production hydrogen peroxide, industry is amplified, 4 tons of these catalyst are packed in 30,000 tons of/year 27.5% hydrogen peroxide commercial plants, reactor inside diameter Φ 1600mm, the bulk density of catalyst is 0.5g/ml, loading height 4200mm, working solution flow are 145m
3/ h, 50 ℃ of reaction temperatures, reaction pressure 0.25MPa, bed resistance 0.01～0.02MPa, 80～90 tons in daily output hydrogen peroxide is compared with using industrial spherical palladium catalyst under the equal process conditions, when equivalent production capacity and equal anthraquinone degradation rate, use hollow irregular shape catalyst of the present invention and can make the bed resistance descend 30～50%, and adorn catalyst 25～30% less.
Embodiment 5
The catalyst for preparing among the embodiment 2 is applied to the industrial production hydrogen peroxide, industry is amplified, and 19 tons of these catalyst is packed in 80,000 tons of/year 27.5% hydrogen peroxide commercial plants reactor inside diameter Φ 2800mm, catalyst bulk density 0.5g/ml, working solution flow 430m
3/ h, 50 ℃ of reaction temperatures, reaction pressure 0.20MPa, bed resistance 0.01MPa, 240 tons in daily output hydrogen peroxide.And under the equal operating condition and connect another reactor, wherein loading 25 tons of industrial spherical palladium catalysts, 240 tons in daily output hydrogen peroxide records bed resistance a 0.09～0.10MPa.
Claims (10)
1. a load type palladium catalyst that is used for process for prepairng hydrogen peroxide by anthraquinone is characterized in that, the carrier of this catalyst is hollow special-shaped carrier, and the content of active component palladium is 0.05%～0.7%.
2. load type palladium catalyst according to claim 1 is characterized in that, described carrier is a silica.
3. load type palladium catalyst according to claim 2 is characterized in that, described silica is indefinite form silica.
4. load type palladium catalyst according to claim 1 is characterized in that, described carrier is the mixture of aluminium oxide or aluminium oxide and silica.
5. load type palladium catalyst according to claim 4 is characterized in that described aluminium oxide is for containing α-Al
2O
3The mixing phase alumina.
6. according to each described load type palladium catalyst of claim 1～5, it is characterized in that described hollow special-shaped carrier comprises: Raschig ring, Wheel ring packing, θ ring, porous bar or porous ring carrier.
7. the preparation method of each described load type palladium catalyst of claim 1～6, the method comprising the steps of: hollow special-shaped carrier is placed the palladium salting liquid, make it to flood active component palladium; This carrier oven dry back of having flooded active component palladium 400～600 ℃ of roastings 2～6 hours, is promptly obtained described load type palladium catalyst.
8. the preparation method of load type palladium catalyst according to claim 7 is characterized in that, described palladium salting liquid is the aqueous solution of palladium bichloride or the aqueous solution of palladium.
9. the preparation method of load type palladium catalyst according to claim 7 is characterized in that, described sintering temperature is 500～550 ℃, and roasting time is 3～4 hours.
10. the method for a process for prepairng hydrogen peroxide by anthraquinone is characterized in that, this method comprises uses each described load type palladium catalyst with hollow special-shaped carrier of claim 1～6 to implement the anthraquinone hydrogenation reaction as catalyst.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2007100629988A CN101229513A (en) | 2007-01-24 | 2007-01-24 | Supported palladium catalyst used for anthraquinone producing peroxid and preparing method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2007100629988A CN101229513A (en) | 2007-01-24 | 2007-01-24 | Supported palladium catalyst used for anthraquinone producing peroxid and preparing method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN101229513A true CN101229513A (en) | 2008-07-30 |
Family
ID=39896497
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNA2007100629988A Pending CN101229513A (en) | 2007-01-24 | 2007-01-24 | Supported palladium catalyst used for anthraquinone producing peroxid and preparing method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101229513A (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102173391A (en) * | 2011-01-15 | 2011-09-07 | 王继华 | Method for producing H2O2 with Pa catalytic agent in working solution containing three solvents |
| CN102219189A (en) * | 2010-04-13 | 2011-10-19 | 中国石油化工股份有限公司 | Method for preparing hydrogen peroxide by adding hydrogen in anthraquinone |
| CN102389799A (en) * | 2011-09-19 | 2012-03-28 | 傅骐 | Palladium catalyst for production of H2O2 by using fixed bed anthraquinone method and preparation method thereof |
| CN103769180A (en) * | 2012-10-24 | 2014-05-07 | 中国石油化工股份有限公司 | Anthraquinone hydrogenation catalyst, preparation method and application thereof |
| CN107185529A (en) * | 2017-06-20 | 2017-09-22 | 武汉理工大学 | It is a kind of to prepare the template that anthraquinone hydrogenation produces peroxidating catalyst for hydrogen |
| CN108070265A (en) * | 2016-11-09 | 2018-05-25 | 中国石油化工股份有限公司 | A kind of preparation method of modifying agent mother liquor and road asphalt |
| CN109833869A (en) * | 2017-11-29 | 2019-06-04 | 中国科学院大连化学物理研究所 | A kind of slurry bed hydrogenation catalyst and its preparation method and application |
-
2007
- 2007-01-24 CN CNA2007100629988A patent/CN101229513A/en active Pending
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102219189A (en) * | 2010-04-13 | 2011-10-19 | 中国石油化工股份有限公司 | Method for preparing hydrogen peroxide by adding hydrogen in anthraquinone |
| CN102173391A (en) * | 2011-01-15 | 2011-09-07 | 王继华 | Method for producing H2O2 with Pa catalytic agent in working solution containing three solvents |
| CN102389799A (en) * | 2011-09-19 | 2012-03-28 | 傅骐 | Palladium catalyst for production of H2O2 by using fixed bed anthraquinone method and preparation method thereof |
| CN102389799B (en) * | 2011-09-19 | 2012-11-14 | 傅骐 | Palladium catalyst for production of H2O2 by using fixed bed anthraquinone method and preparation method thereof |
| CN103769180A (en) * | 2012-10-24 | 2014-05-07 | 中国石油化工股份有限公司 | Anthraquinone hydrogenation catalyst, preparation method and application thereof |
| CN108070265A (en) * | 2016-11-09 | 2018-05-25 | 中国石油化工股份有限公司 | A kind of preparation method of modifying agent mother liquor and road asphalt |
| CN107185529A (en) * | 2017-06-20 | 2017-09-22 | 武汉理工大学 | It is a kind of to prepare the template that anthraquinone hydrogenation produces peroxidating catalyst for hydrogen |
| CN107185529B (en) * | 2017-06-20 | 2019-10-11 | 武汉理工大学 | A kind of template preparing anthraquinone hydrogenation production peroxidating catalyst for hydrogen |
| CN109833869A (en) * | 2017-11-29 | 2019-06-04 | 中国科学院大连化学物理研究所 | A kind of slurry bed hydrogenation catalyst and its preparation method and application |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Bi et al. | Efficient degradation of toluene over ultra-low Pd supported on UiO-66 and its functional materials: Reaction mechanism, water-resistance, and influence of SO2 | |
| CN101229513A (en) | Supported palladium catalyst used for anthraquinone producing peroxid and preparing method thereof | |
| CN101612581B (en) | Mesoporous-macroporous integral catalyst for purifying CO in hydrogen-rich gas and preparation | |
| CN103071487A (en) | Hydrogenation catalyst for anthraquinone process fixed bed and preparation method of hydrogenation catalyst | |
| CN109529821B (en) | Palladium-based catalyst for thermal catalysis of formaldehyde degradation | |
| CN104338550B (en) | A kind of preparation method for handling dust technology and the catalyst for generating alkyl nitrite | |
| CN104549236A (en) | Hydrogenation catalyst and application thereof | |
| CN104368336A (en) | Monolithic catalyst for hydrogen peroxide production through pentylanthraquinone process and preparation method thereof | |
| CN109833901A (en) | A kind of high-dispersion loading type slurry bed hydroprocessing beaded catalyst and preparation method thereof | |
| CN108067220A (en) | A kind of hydrogen peroxide synthesis loaded catalyst and its preparation method and application | |
| CN102658149A (en) | Copper oxide catalyst for preparing chlorine gas from chlorine hydride by catalytic oxidation, and preparation method and application thereof | |
| CN101229915A (en) | Method for producing hydrogen peroxide by anthraquinone process | |
| CN105797719A (en) | Load type duplex metal/multi-metal catalyst for hydrogenation synthesis of metanilic acid from m-Nitrobenzenesulfonic acid and preparation method and application | |
| CN113731405A (en) | Catalyst for preparing hydrogen peroxide by anthraquinone hydrogenation and preparation method and application thereof | |
| CN106881084B (en) | One kind is for reverse water-gas-shift reaction noble metal catalyst and its preparation and application | |
| CN105732284A (en) | Selective hydrogenation method for C3 fraction | |
| CN109926046B (en) | Catalyst for hydrogen production by hydroiodic acid decomposition and preparation method thereof | |
| CN112191244A (en) | Activated carbon-supported gold-based catalyst, preparation method thereof and application thereof in acetylene hydrogenation | |
| CN103301851A (en) | Preparation method for anthraquinone hydrogenation catalyst | |
| US11390522B2 (en) | Process for conversion of sulfur trioxide and hydrogen production | |
| CN113134372B (en) | CO-resistant anthraquinone hydrogenation catalyst and preparation method thereof | |
| CN105478150A (en) | Alkali catalyst with multilayer structure and preparation method and application thereof | |
| CN113135818B (en) | Method for hydrogenating alkyl anthraquinone | |
| CN112439432B (en) | Anthraquinone hydrogenation catalyst and preparation method thereof | |
| CN107855125A (en) | The preparation method of nano-nickel oxide |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C12 | Rejection of a patent application after its publication | ||
| RJ01 | Rejection of invention patent application after publication |
Open date: 20080730 |